Background, aim, and scope Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters. Materials and methods The PPCPs were selected on the basis of consumption at the regional scale, reported aquatic toxicity, and the suitability of the gas chromatography/mass spectrometry (GC/MS) method for the determination of the compounds at trace levels. The studied PPCPs, caffeine (stimulant), carbamazepine (antiepileptic), pentoxifylline (anticoagulant), cyclophosphamide (cytostatic), ibuprofen (analgesic), and galaxolide (musk fragrance), were determined in samples of the Somes River. The analytes were enriched by solid-phase extraction and subsequently determined by GC/MS. Caffeine, pentoxifylline, and galaxolide were determined underivatized, whereas the acidic pharmaceuticals carbamazepine, cyclophosphamide, and ibuprofen were determined after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide. Results and discussion The concentrations in the Somes River varied from below 10 ng/L up to 10 μg/L. A substantial decrease of the exposure in the Somes River could be observed due to the upgrade of the municipal WWTP in Cluj-Napoca. The loads in the river stretch between Cluj-Napoca and Dej (Somes Mic) varied strongly: caffeine (400-2,000 g/day), carbamazepine (78-213 g/day), galaxolide (140-684 g/day), ibuprofen (84-108 g/day). After the upgrade of the WWTP Cluj-Napoca, the concentrations in the Somes of caffeine, pentoxifylline, cyclophosphamide, galaxolide, and tonalide were significantly reduced (over 75%). One might be cautious comparing both studies because the relative efficiency of the WWTP's removal of PPCP was not evaluated. However, the significantly lower concentrations of most compounds after the upgrade of the WWTP Cluj-Napoca allow one to infer that the technical measures at the source substantially reduced inputs of contaminants to the receiving river. Dej loads of the poorly biodegradable substance carbamazepine increased by a factor of 2-3 as a result of wastewater discharges into the river. The disproportionate increase in caffeine loads by a factor of 4 below Cluj-Napoca indicates inputs of untreated wastewater from the Somes Mare due to the discharge of untreated wastewater derived from Bistrita, Nasaud, and Beclean (115,000 inhabitants). Conclusions The relative contribution of treated and untreated wastewater in surface water might be assessed by measuring chemical markers. Recalcitrant pharmaceuticals like carbamazepine are suitable as chemical markers for estimating the relative contribution of wastewater in surface water. The easily degradable caffeine might be a good indicator for raw sewage and hardly treated wastewaters. Recommendations and perspectives Municipal WWTPs have the potential of a significant contribution in reducing the load of contaminants to ambient waters. The efficiency of the wastewater treatment in Cluj-Napoca improved considerably after the upgrade of the WWTP. Therefore, it is crucial that several WWTPs must be implemented or improved in the Somes Valley Watershed in order to reduce the discharge of contaminants in the Somes River from these point sources.

Background, aim and scope Sulphonated anthraquinones are precursors of many synthetic dyes and pigments, recalcitrant to biodegradation and thus not eliminated by classical wastewater treatments. In the development of a phytotreatment to remove sulphonated aromatic compounds from dye and textile industrial effluents, it has been shown that rhubarb (Rheum rabarbarum) and common sorrel (Rumex acetosa) are the most efficient plants. Both species, producing natural anthraquinones, not only accumulate, but also transform these xenobiotic chemicals. Even if the precise biochemical mechanisms involved in the detoxification of sulphonated anthraquinones are not yet understood, they probably have cross talks with secondary metabolism, redox processes and plant energy metabolism. The aim of the present study was to investigate the possible roles of cytochrome P450 monooxygenases and peroxidases in the detoxification of several sulphonated anthraquinones. Materials and methods Both plant species were cultivated in a greenhouse under hydroponic conditions, with or without sulphonated anthraquinones. Plants were harvested at different times and either microsomal or cytosolic fractions were prepared. The monooxygenase activity of cytochromes P450 toward several sulphonated anthraquinones was tested using a new method based on the fluorimetric detection of oxygen consumed during cytochromes P450-catalysed reactions. The activity of cytosolic peroxidases was measured by spectrophotometry, using guaiacol as a substrate. Results A significant activity of cytochromes P450 was detected in rhubarb leaves, while no (rhizome) or low (petioles and roots) activity was found in other parts of the plants. An induction of this enzyme was observed at the beginning of the exposition to sulphonated anthraquinones. The results also indicated that cytochromes P450 were able to accept as substrate the five sulphonated anthraquinones, with a higher activity toward AQ-2,6-SS (0.706 nkat/mg protein) and AQ-2-S (0.720 nkat/mg protein). An activity of the cytochromes P450 was also found in the leaves of common sorrel (1.212 nkat/mg protein (AQ-2,6-SS)), but no induction of the activity occurred after the exposition to the pollutant. The activity of peroxidases increased when rhubarb was cultivated in the presence of the five sulphonated anthraquinones (0.857 nkat/mg protein). Peroxidase activity was also detected in the leaves of the common sorrel (0.055 nkat/mg protein), but in this plant, no significant difference was found between plants cultivated with and without sulphonated anthraquinones. Discussion Results indicated that the activity of cytochromes P450 and peroxidases increased in rhubarb in the presence of sulphonated anthraquinones and were involved in their detoxification mechanisms. Conclusions These results suggest the existence in rhubarb and common sorrel of specific mechanisms involved in the metabolism of sulphonated anthraquinones. Further investigation should be performed to find the next steps of this detoxification pathway. Recommendations and perspectives Besides these promising results for the phytotreatment of sulphonated anthraquinones, it will be of high interest to develop and test, at small scale, an experimental wastewater treatment system to determine its efficiency. On the other hand, these results reinforce the idea that natural biodiversity should be better studied to use the most appropriate species for the phytotreatment of a specific pollutant.

Background, aim, and scope Decabromodiphenyl ether (DecaBDE) is used as an additive flame retardant in polymers. It has become a ubiquitous environmental contaminant, particularly abundant in abiotic media, such as sediments, air, and dust, and also present in wildlife and in humans. The main DecaBDE constituent, perbrominated diphenyl ether (BDE-209), is susceptible to transformations as observed in experimental work. This work is aimed at identifying and assessing the relative amounts of products formed after UV irradiation of BDE-209. Materials and methods BDE-209, dissolved in tetrahydrofuran (THF), methanol, or combinations of methanol/water, was exposed to UV light for 100 or 200 min. Samples were analyzed by gas chromatography/mass spectrometry (electron ionization) for polybrominated diphenyl ethers (PBDEs), dibenzofurans (PBDFs), methoxylated PBDEs, and phenolic PBDE products. Results The products formed were hexaBDEs to nonaBDEs, monoBDFs to pentaBDFs, and methoxylated tetraBDFs to pentaBDFs. The products found in the fraction containing halogenated phenols were assigned to be pentabromophenol, dihydroxytetrabromobenzene, dihydroxydibromodibenzofuran, dihydroxytribromodibenzofuran, and dihydroxytetrabromodibenzofuran. The PBDEs accounted for approximately 90% of the total amount of substances in each sample and the PBDFs for about 10%. Discussion BDE-209 is a source of PBDEs primarily present in OctaBDEs but also to some extent in PentaBDEs, both being commercial products now banned within the EU and in several states within the USA. It is notable that OH-PBDFs have not been identified or indicated in any of the photolysis studies performed to date. Formation of OH-PBDFs, however, may occur as pure radical reactions in the atmosphere. Conclusions Photolysis of decaBDE yields a wide span of products, from nonaBDEs to hydroxylated bromobenzenes. It is evident that irradiation of decaBDE in water and methanol yields OH-PBDFs and MeO-PBDFs, respectively. BDE-202 (2,2',3,3',5,5',6,6'-octabromodiphenyl ether) is identified as a marker of BDE-209 photolysis. Recommendations and perspectives BDE-209, the main constituent of DecaBDE, is primarily forming debrominated diphenyl ethers with higher persistence which are more bioaccumulative than the starting material when subjected to UV light. Hence, DecaBDE should be considered as a source of these PBDE congeners in the environment.

Background, aim, and scope Endosulfan, an organochlorine pesticide (OCP), is genotoxic in mammalian cells and generally considered to be toxic and classified by the World Health Organization and the US Environmental Protection Agency as priority pollutants and a nominator for inclusion in a future iteration of the persistent organic pollutants treaty. Endosulfan is a currently used pesticide and still being used worldwide. The general trend of total global endosulfan use has increased continuously since the first year when this pesticide was applied. It is critical to create national endosulfan usage/emission inventories for China to carry out source-receptor relation analysis, risk assessment, and other research related to endosulfan in this country. Chinese inventories have been published for some OCPs, such as technical HCH and lindane, DDT, and chlordane; for endosulfan, however, there has not been any usage inventory available on any scales (national or provincial), although endosulfan has been widely used since 1994 in this country. This is the first part of the work. The goal of this paper is to quantify the historical production and usage of endosulfan in China and to compile gridded historical usage inventories of endosulfan for this country. Based on these usage inventories, emission and residue inventories will be created, which is the goal of the second part of the work. Materials and methods Due to the lack of national production and usage information of endosulfan in China, a method to estimate the use of endosulfan was developed. First, information of crops on which endosulfan is applied and average endosulfan use and annual application frequencies of endosulfan on these crops were collected. Secondly, usage of endosulfan on each crop was estimated using the national cropland area for each province from Chinese government reports. Finally, with the help of GIS (geographic information system), the usage data of this insecticide was allocated to a grid system, with a 1/4° longitude by 1/6° latitude resolution, with a size for each grid cell of approximately 25 km by 25 km. Results and discussion The use of endosulfan in agriculture in China started on cotton in 1994, and on wheat, tea, tobacco, apples, and other fruits in 1998. Endosulfan usage on cotton, wheat, tea, tobacco, and apples in China has been estimated to be approximately 25,700 t between 1994 and 2004. The province with the highest usage of endosulfan is Henan Province, with a total usage reaching 4,000 t, followed by the uses in Xinjiang Autonomous Region (3,200 t), Shandong Province (3,000 t), Hebei Province (2,100 t), and Anhui Province (1,900 t). Gridded usage inventories of endosulfan at a 1/4° longitude by 1/6° latitude resolution have been created, which indicate that the intensive endosulfan use was in the south of Hebei Province, west of Shandong Province, east of Henan Province, north of Anhui Province, east of Jiangsu Province, and some areas in Yunnan Province and Xinjiang Autonomous Region. General agreement has been found between the usage data from our estimation and the small amount of usage data published in China. Conclusions This is the first national gridded endosulfan usage inventory produced for China. The annual applications of endosulfan from 1994 to 2004 in China were estimated based on the total areas of major crops, on which endosulfan was applied, and spatial distribution of the application was generated at provincial and prefecture levels. With the help of GIS, endosulfan usage based on prefecture was transferred to a 1/4° longitude by 1/6° latitude gridding system. The satisfaction of the inventories was supported by the consistence between the estimation of the annual usage and the reported annual production of endosulfan. Recommendations and perspectives This gridded endosulfan usage inventory created in this study will be improved upon availability of new information of endosulfan. The usage inventories can be used to create gridded emission and residue inventories for this insecticide. It is believed that this work will pave the way for further endosulfan studies in China and beyond.

Background, aim, and scope Lindane, technically 1, 2, 3, 4, 5, 6-hexachlorocyclohexane (γ- HCH), is the most commonly detected organochlorine pesticide from diverse environmental compartments. Currently, India is the largest consumer and producer of lindane in the world. The production of lindane results in the generation of large quantities of waste HCH isomers (mainly α-, β- and δ-). All these isomers are toxic and have a long-range environmental transport potential. The aim of this study was to monitor the seasonal variation of HCH isomers in an open soil-plant-rhizospheric soil system of a contaminated industrial area. For this, selected plant species and their rhizospheric soil (soil samples collected at a depth range of 0-45 cm near to the root system) and open soil samples (soil samples collected (0-30 cm depth) from 1-1.5 m away from the plant root system) were collected for 2 years (two summer seasons and two winter seasons). Materials and methods Seven plant species along with their rhizospheric soil and open soil samples were collected seasonally from different parts of the industry. Plant samples were separated into root, leaf and stem. HCH isomers in plant and soil samples were extracted by matrix solid-phase dispersion extraction (MSPD) and Soxhlet extraction, respectively, followed by GC-ECD. The seasonal difference in occurrence of HCH isomers in plant samples with their respective soil-system was studied by multivariate statistical approaches. Results The mean concentration of total HCH in plant samples, open soil and rhizospheric soil samples were found in the range of 14.12 to 59.29 mg kg⁻¹; 38.64 to 104.18 mg kg⁻¹ and 8.38 to 26.05 mg kg⁻¹, respectively. Cluster grouping reveals that S. torvum and W. somnifera can accumulate more HCH than other studied species. Discussion There was a marked seasonal difference in the occurrence of HCH isomers in plant samples (p < 0.05) and open soil samples (p < 0.01). Comparatively higher levels of HCH isomers were detected from plant samples during summer, while higher levels of HCH isomers were detected from soil samples during the winter season. There was no significant difference in seasonal variation of HCH isomers in rhizospheric soil samples; however, total HCH in rhizospheric soil samples were 4 to 5-fold lower than the open soil samples. The total concentration of HCH isomers in roots is linearly related to their rhizospheric HCH level. Conclusions HCH isomers were detected in open soil, plants and rhizospheric soil samples. Monitoring studies clearly revealed that the above-mentioned industrial area is contaminated with all major isomers of HCH. Occurrence of all these isomers in the study area point out the lack of sustainable management practices of this industry for protecting the area from hazardous waste. The analytical results confirmed that accumulation depends upon the plant species, soil and climatic conditions. Recommendations and perspectives Recently, α-, β- and γ-HCH have been nominated by the POPs Reviewing Committee for inclusion into the Stockholm Convention to address the HCH contamination on a global level. Therefore, there is an urgent need to stop the production of lindane and remediate contaminated soil sites. Based on the monitoring studies, the promising species like W. somnifera and S. torvum may be selected for the on-site phytoremediation of HCH-contaminated soil. The mismanagement of HCH residues from the organochlorine industry and their contemporary relevance often after decades of their deposition is one key example demonstrating the necessity to evaluate the waste deposits of the respective organochlorine productions and need for a strict waste management, and the necessity of an integrated pollution prevention and control strategy for the whole organochlorine industry including also the developing countries.

Background Modern societies depend on environmental sustainability and on new generations of individuals well-trained by environmental research and teaching institutions. In the past, significant contributions to the identification, assessment, and management of chemical stressors with legal consequences have been made. Main Features Within this article, we intend to elucidate the merits and the emerging challenges of chemicals-related environmental sciences. The manuscript is supported by more than 70 professors and university academics of leading institutions in Germany, Switzerland, Austria, and other countries in Europe, but addresses topics of global concern. Results and Discussion Many environmental problems of pollutants remain to be addresses, since new chemical compounds or classes of new compounds are continuously developed and brought to the market and sooner or later “emerge” in the environment. Further issues are the inclusion of transformation products and chemical mixtures in environmental risk assessment, the long-term presence of xenobiotics bound to soils and sediments, as well as an understanding of the ecological relevance of ecotoxicological end points. Conclusion and Perspectives We point out the need for a strong academic research and education system in chemicals-related environmental sciences to ministries, politicians, and research funding institutions and we propose to create specific units in the national funding bodies that address basic and interdisciplinary research in this field.

Background, aim, and scope Ten years of public health interventions on industrial emissions to clean air were monitored for the Mediterranean city of Cartagena. During the 1960s, a number of large chemical and non-ferrous metallurgical factories were established that significantly deteriorated the city's air quality. By the 1970s, the average annual air concentration of sulfur dioxide (SO₂) ranged from 200 to 300 μg/m³ (standard conditions units). In 1979, the Spanish government implemented an industrial intervention plan to improve the performance of factories and industrial air pollution surveillance. Unplanned urban development led to residential housing being located adjacent to three major factories. Factory A produced lead, factory B processed zinc from ore concentrates, and factory C produced sulfuric acid and phosphates. This, in combination with the particular abrupt topography and frequent atmospheric thermal inversions, resulted in the worsening of air quality and heightening concern for public health. In 1990, the City Council authorized the immediate intervention at these factories to reduce or shut down production if ambient levels of SO₂ or total suspended particles (TSP) exceeded a time-emission threshold in pre-established meteorological contexts. The aim of this research was to assess the appropriateness and effectiveness of the intervention plan implemented from 1992 to 2001 to abate industrial air pollution. Materials and methods The maximum daily 1-h ambient air level of SO₂, NO₂, and TSP pollutants was selected from one of the three urban automatic stations, designed to monitor ambient air quality around industrial emissions sources. The day on which an intervention took place to reduce and/or interrupt industrial production by factory and pollutant was defined as a control day, and the day after an intervention as a post-control day. To assess the short-term intervention effect on air quality, an ecological time series design was applied, using regression analysis in generalized additive models, focusing on day-to-day variations of ambient air pollutants levels. Two indicators were estimated: (a) appropriateness, the ratio between mean levels of the pollutant for control days versus the other days, and (b) effectiveness, the ratio between mean levels of the pollutant for post-control days versus the other days. Ratios in regression analyses were adjusted for trend, seasonality, temperature, humidity and atmospheric pressure, calendar day, and special events as well as the other pollutants. Results A total of 702 control days were made on the factories' industrial production during the 10-year period. Fifteen reductions and five shutdown control days took place at factory A for ambient air SO₂. At factory B, more controls were carried out for the SO₂ pollutant in the years 1992-1993 and 1997. At factory C, the control days for SO₂ decreased from 59 reductions and 14 shutdowns to a minimum from 1995 onwards, whereas the controls on TSP were more frequent, reaching a maximum of 99 reductions and 47 shutdowns in the last year. SO₂ ambient air mean levels ranged from 456 to 699 μg/m³ among factories on reduction control days and between 624 and 1,010 μg/m³ on shutdown days. The TSP ambient air mean levels were 428 and 506 μg/m³ on reduction and shutdown days, respectively. For all types of control days and factories, a mean ratio of 104% (95% confidence interval [CI] 88 to 121) in SO₂ levels was obtained and a mean ratio of 67% (95% CI 59 to 75) in TSP levels. Post-control days at all factories showed a mean ratio of -16% (95% CI -7 to -24) in SO₂ levels and a mean ratio of -13% (95% CI -7 to -19) in TSP levels. Discussion Interventions on industrial production based on the urban SO₂ and TSP ambient air levels were justified by the high concentrations detected. The best assessment of the interventions' effectiveness would have been to utilize the ambient air pollutant concentration readings from the entire time of the production shutdowns or reductions; however, the daily hourly maximum turned out to be a useful indicator because of meteorological factors influencing the diurnal concentration profile. A substantial number of interventions were carried out from 1 to 3 am, when vehicular traffic was minimum. On the other hand, atmospheric stability undergoes diurnal cycling in the autumn-winter period due to thermal inversion, which reaches maximum levels around daybreak. Therefore, this increases the ambient air levels and justified the interventions carried out at daybreak in spite of the traffic influence. Conclusions All the interventions for SO₂ and TSP were carried out when the measured ambient air levels of pollutants were exceeded, which shows the appropriateness of the intervention program. This excess was greater when intervening on SO₂ than on the TSP levels. For both ambient air levels of SO₂ and TSP, significant drops in air pollution were achieved from all three factories following activity reductions. The production shutdown controls were very effective, because they returned excess levels, higher than in the reduction controls, to everyday mean values. Recommendations and perspectives The Cartagena City observational system of intermittent control has proven to effectively reduce industrial emissions' impact on ambient air quality. This experienced model approach could serve well in highly polluted industrial settings. From a public health perspective, studies are needed to assess that the industrial interventions to control air pollution were related to healthier human populations. Legislation was needed to allow the public administration to take direct actions upon the polluting industries.

Background, aim, and scope The possibility of gene transfer from genetically modified oilseed rape (OSR) to its cultivated or wild relatives is of concern since its commercial cultivation, because of its potential weediness and impact on the environment. Introgression of modified genes can affect conservation of agricultural crops, because there are many cultivars and wild Brassicaceae that may cross with genetically modified OSR (Brassica napus) in Japan. Japan imports more than 2 million tons of OSR a year from Canada and other countries. Since volunteers of GM OSR were found around harbors in 2004, a lot of feral GM OSR was discovered in Japan. To consider the way how to keep domestic Brassicaceae from GM contamination, we surveyed and analyzed the dispersal and persistence of GM OSR around Japanese harbors. We present the cause and abundance of GM OSR in Japan by this paper. Materials and methods Survey of the feral OSR was performed several times a year at different seasons when domestic OSR either grows or does not around port areas. Detection of herbicide tolerance in feral B. napus was done by test papers that cross react with the modified gene product. Two kinds of herbicide tolerance (glyphosate and glufosinate) were tested. Results The feral B. napus were discovered around all 13 harbors that import rapeseeds from foreign countries. Genetically modified, herbicide-tolerant OSR were frequently found in the surveyed populations. Two kinds of herbicide-tolerant OSR (glyphosate- and glufosinate-tolerant) were discovered in a natural condition 40 km from port to an oil factory where 60,000 tons of OSR seed are processed a year. The cause of voluntary growth of OSR is seed spillage during transportation by trucks from harbors to oil factories and other processing facilities. Some of the feral OSR growing along the roadsides of transport paths exhibited perennial growth spilling their seeds around the places. Alteration of the generation of feral GM OSR was discovered for the first time in Japan as a result of this study. We studied the yearly change of feral OSR abundances focusing on Yokkaichi port over the 4 years since 2004. The rate of GM OSR increases year to year, and reaches nearly 90% in 2008. Discussion The possibility and consequences of gene transfer from the genetically modified OSR to domestic species (B. rapa and B. juncea) were discussed in relation to impact on domestic agriculture and on environments. Evolutional meaning of the gene transfer was also discussed with respect to the gene construct of GM OSR. This study shows the importance of another pathway of modified gene transfer to non-GM relative species by seed transportation in addition to pollen transfer from commercial cultivation of genetically modified OSR. Conclusions and recommendations We identified unintended dispersal and persistence of GM OSR around Japanese harbors that import OSR from Canada and other countries. Both glyphosate- and glufosinate-tolerant feral B. napus were discovered. The cause of volunteer OSR is spillage of the seeds during transportation by truck to oil factory. The feral GM OSR sometimes showed perennial growth in Japanese phonological conditions which are not observed for domestic Brassicaceae. In addition, we confirmed an alteration of generations by feral GM OSR in Japan. The possibility of cross pollination and GM gene introgression to domestic varieties can occur in these environments. To improve the situation, each responsible organization, company, administration, or government should establish measures how to stop the dispersal and persistence of GM OSR in nature. Also, the GM plant developers are responsible for revising this situation.